CN108541265A - The method of oxide protective layer on sealing metal base material - Google Patents
The method of oxide protective layer on sealing metal base material Download PDFInfo
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- CN108541265A CN108541265A CN201680024282.6A CN201680024282A CN108541265A CN 108541265 A CN108541265 A CN 108541265A CN 201680024282 A CN201680024282 A CN 201680024282A CN 108541265 A CN108541265 A CN 108541265A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/08—Copolymers of ethene
- C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09D123/0869—Acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/007—After-treatment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/08—Copolymers of ethene
- C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09D123/0869—Acids or derivatives thereof
- C09D123/0876—Neutralised polymers, i.e. ionomers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Metallurgy (AREA)
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- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
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Abstract
The present invention relates to a kind of methods using the oxide protective layer on water-based composition sealing metal base material; the water-based composition includes at least one aliphatic water-dispersed and/or water dissolution form and acyclic olefin and at least one α; the copolymer or copolymer mixture of β unsaturated carboxylic acids; the acid value of the wherein described copolymer or copolymer mixture is at least 20mg KOH/g, but is no more than 200mg KOH/g.Particularly, it is used to seal the purposes of the protective layer of the oxide and/or hydroxide based on elements Si, Ti and/or Zr on aluminium base the invention further relates to this copolymer or this copolymer mixture, wherein the thickness of the protective layer is at least 2 μm.
Description
It is described aqueous the present invention relates to a kind of method using the oxide protective layer on water-based composition sealing metal base material
Composition includes at least one aliphatic water-dispersed and/or water dissolution form and acyclic olefin and at least one α, β-unsaturation
The copolymer or copolymer mixture of carboxylic acid, wherein the acid value of the copolymer or copolymer mixture is at least 20mg KOH/
G, but it is no more than 200mg KOH/g.Particularly, the invention further relates to this copolymers or this copolymer mixture for sealing
The purposes of the protective layer of the oxide and/or hydroxide based on elements Si, Ti and/or Zr on aluminium base, wherein the guarantor
The thickness of sheath is at least 2 μm.
On metal base, especially aluminium electrolytically generated oxide skin(coating) be widely used in the prior art generate it is anticorrosive
And/or the method for decorative coating, such as use anodic oxidation or plasma electrolysis deposition method.Electrolytically generated oxidation is protected
Sheath protects metal material from corrosion and weathering, and usually also increases the case hardness of component made of these materials and resistance to
Mill property.
In the case of anode oxidation method, the electrolytic oxidation nitride layer on aluminium base can be obtained by applying anode potential
, be substantially made of the oxide of aluminium and hydroxide, plasma electrolysis method also generates oxide skin(coating), substantially by
The oxide and hydroxide of the metallic element being present in electrolyte generated due to electrolyte decomposition in the plasma
Composition.In addition, other than aluminium or with the material of aluminium layer, it, can also be by oxidation protection when using plasma electrolysis method
Layer is applied on other materials such as magnesium, titanium and zinc.It is described in WO 2003/029529 for material magnesium and aluminium, application is based on
The classicalpiston electrolytic method of the protective layer of titanium oxide.
The electrical general condition of anode oxidation method is usually significantly deviating from the plasma for generating oxide protective layer
The general condition of electrolytic method.When carrying out anode oxidation method, as the function of electrolyte, current density 1-2A/dm2,
Voltage is no more than 25V, and generates the electrolytically generated protective layer of the plasma with similar layer thickness on aluminium with pulse operation, makes
With the crest voltage no more than 500V, wherein average power density is 5-10A/dm2.With the thickness for the protective layer that electrolysis applies
It can substantially be variably set, however for the property of oxide protective layer, need at least 2 μm of layer thickness in exposure
Etch-proof protection is provided in moisture or while being contacted with liquid, wherein the typical layer thickness for meeting industrial requirements is 5-50 μm.
Here the method for the application oxide protective layer summarized has in common that, since the deposition process is in electrolysis item
The property carried out under part, therefore porous layer is formed, these layers cannot provide lasting effective protection for high-corrosion medium.It is logical
Often, newly-generated oxide protective layer is modified in different ways to seal hole in the prior art.After the electrolytic process this
A little processes are referred to as bonding or be sealed in technical term.In principle, no matter its manufacturing method, any porous oxidation protection
Layer can be sealed.However, specific dressing method has become the common method to form oxide protective layer, and metal base
Usually coated with these methods.In the presence of the method for the determination for sealing, especially for the oxygen for being electrolysed application on aluminum substrates
Change protective layer, such as cold sealing in the presence of metallic catalyst or the heat seal using water-based composition.
In general, inorganic compound is added in sealing bath, the hydrolysis of porous alumina layer is accelerated and is caused other
At least surface of layer structure oxide or oxide skin(coating) is modified.Sealing bath in the prior art can contain water-soluble silicic acid
Salt, additionally to increase the corrosion resistance (US 6,686,053 of oxide skin(coating)；1 873 278 A1 of EP) or preparing lithographic plate print
Make material surface hydrophiling (US 3,181,461, US 2,714,066) when brush version.
In certain application fields, sealing porous oxide protective layer also creates priming paint appropriate.Dependent on be related to hydrolysis,
The conventional seals of the mechanism of bonding during expanding and being subsequently dried seem not being suitable for this purpose, because sealing surfaces are usual
With lower roughness, therefore less anchor point is provided to organic coating.
It is usually obtained by vacuum impregnation by means of the sealing porous material of crosslinking organic resins；However, this method is with non-
Often complicated process.Further, it is necessary to ensure that the sealing suitable for multiple oxide protective layers occurs, to inhibit metal base
Corrosion.In general, hot and cold encapsulating method well known in the prior art is not (for example, lead to the protective layer based on titanium oxide
Any follow-up bonding) and crosslinked arbitrary organic resin is unable to complete this task in the hole of oxide protective layer.
WO 2012/174386 describes the purpose for sealing and assigning low-friction coefficient, with the moisture of polyurethane resin
Dispersion liquid handles the protective layer based on titanium oxide of the plasma electrolysis deposition on aluminium.Where it is proposed the aluminum materials so handled
The cylinder jacket that can be used in the crankcase of internal combustion engine.
The purpose of the present invention is developing the method for sealing porous protective layer, it can be used for being effectively protected various metals base material
From the infringement of high-corrosion medium.Particularly, this method will be used to have the oxide based on elements Si, Ti and/or Zr
And/or the aluminium base of the protective layer of hydroxide.In addition, the method allows to by such as spraying the routine painting with dip-coating
Cloth method applies the sealing medium.
The purpose is realized by the method for the oxide protective layer on sealing metal base material herein, wherein making to have described
The metal base of protective layer is in contact with following substances：
(i) it is used for the water-based composition of sealing, it includes
A) water-based composition, at least one fat water-dispersed and/or water dissolution form of at least 1 weight % are based on
Race and acyclic olefin and at least one α, the copolymer or copolymer mixture of beta-unsaturated carboxylic acid, wherein the copolymer or total
The acid value of copolymer mixture is at least 20mg KOH/g, but is no more than 200mg KOH/g；With
B) crosslinking agent,
And then
(ii) it is dried and/or cures in the case where providing thermal energy,
Wherein, it is measured using 4mm DIN flow cups, in step (i) not for the flowing time of the water-based composition of sealing
More than 50 seconds.
According to the present invention, sealing refers to one or more processing steps comprising at least one wet-chemical treatment step,
Suitable for reducing the porosity of the protective layer and/or reducing free substrate surface.As long as in the wet-chemical treatment step
In there are a certain amount of film-forming organic polymers, there is this applicability.
According to the present invention, protective layer refer to those of be applied on metal base with the layer thickness more than or equal to 2 μm it is non-
Metal coating, wherein the layer thickness can be determined by eddy-current method, as every square decimeter of at least five measurement point
The contact surface of arithmetic mean of instantaneous value, each measurement point is at least one square millimeter but is no more than one square centimeter.
According to the present invention, protective layer is oxidation, and the coating is substantially based on oxide and/or hydroxide, preferably
The oxide and/or hydroxide of element based on the key component for not being metal base, be based particularly on elements Si, Ti, Zr,
The oxide and/or hydroxide of Nb, Ta and/or Sn, wherein nonmetallic ratio is preferably smaller than 10 atom %.
For being enough a certain amount of film-forming organic polymer sealed, according to the invention it is preferred to such method, wherein base
In the water-based composition, the ratio of the copolymer or copolymer mixture is at least 5 weight %.However, in order to pass through leaching
Stain or spray pattern effectively apply the composition for sealing, it is preferable that the copolymer or copolymer mixture
Ratio is no more than 30 weight %, is particularly preferably no more than 20 weight %, in each case, is all based on described for sealing
Composition.
In this respect, it is necessary to ensure that the viscosity of the composition for sealing passes through no more than certain value under the viscosity
Dipping or spraying, which apply the composition, to be realized by complicated process engineering measure, such as improve and apply temperature or raising
Spray pressure.Therefore, the flowing time measured by 4mm DIN flow cups should be made not surpass for the preparation of the composition of sealing
50 seconds are spent, the preferably described flowing time is no more than 40 seconds.However, in turn, the flowing preferably measured by 4mm DIN flow cups
Time is at least 20 seconds, to ensure that the wet film of sufficient amount is retained on the surface and edge of component to be sealed.The flowing time
It is measured at 20 DEG C according to standard DIN 53211.Those skilled in the art are substantially familiar with setting by rheologic additive viscous
The method of degree.
According to the present invention, polymer is dissolved in water or is dispersed in water, it is assumed that the average grain diameter in water phase is less than 1
μm.The average grain diameter can be according to ISO 13320:2009 are determined by laser diffraction at 20 DEG C, by correspondent composition
The cumulative particle size distribution for being referred to as D50 provides.
According to the present invention, copolymer mixture includes chemistry and/or the different at least one aliphatic of structure and without cyclenes
The copolymer of hydrocarbon and at least one alpha, beta-unsaturated carboxylic acid.In the copolymer mixture of coating formulation according to the present invention,
It can exist simultaneously, for example, comprising different alkene or difference α, copolymer of the beta-unsaturated carboxylic acid as comonomer, Huo Zhe
The copolymer of same comonomer comprising different number in copolymer..
According to the present invention, the acid value is the characteristic value being determined by experiment, and is in copolymer or copolymer mixture
The measurement of the quantity of free acidic group.The acid value is by the way that the copolymer for the amount weighed or copolymer mixture are dissolved in volume ratio
3:In 1 methanol and the solvent mixture of distilled water, then constant-current titration is carried out with the solution of 0.05mol/L KOH in methyl alcohol
To measure.The potential measurement by compound electrode (Metrohm'sWith reference to electrolyte：0.4mol/L
The ethylene glycol solution of tetraethylammonium bromide) it carries out.Acid value corresponds at the inflection point of potentiometric titration curve, every gram of copolymer or total
The addition of KOH in copolymer mixture, as unit of milligram.
If the acid value of the copolymer or copolymer mixture of the alkene and alpha, beta-unsaturated carboxylic acid is less than 20mg KOH/
G, then it is according to the present invention for sealing composition after it cure on the oxide protective layer of metal base do not have enough
Wetability and adhesiveness, therefore be not suitable for sealing the hole of these protective layers.In turn, as the group for sealing
The alkene of sealing component and the acid value of the copolymer of alpha, beta-unsaturated carboxylic acid or copolymer mixture for closing object are higher than 200mg
When KOH/g, do not have sufficient barrier action, metal to the corrosive ion in anhydrous medium after sealing component can be caused to cure
Base material itself does not have perfect shelter.
The weight ratio of aliphatic and acyclic olefin is preferably at least 40 weight % in copolymer or copolymer mixture, special
It You Xuanweizhishao not 60 weight %, preferably more than 95 weight %.Which ensure that solid on oxide protective layer to be sealed
Change and/or dry and include the copolymer or copolymer mixture composition when being in contact with aqueous medium to ion
Permeability is farthest lowered, while enough bondings are also provided to the metal base with the oxide protective layer
Property.
According to the present invention, it is present in the aliphatic of the copolymer or copolymer mixture in the composition for sealing
It is preferably selected from ethylene, propylene, 1- butylene, 2- butylene, isobutene, 1,3- butadiene and/or 2- methyl-1s, 3- fourths with acyclic olefin
Diene (2-methylbuta-1,3-diene), particularly preferred ethylene and/or propylene.
According to the present invention, it is present in the α of the copolymer or copolymer mixture in the composition for sealing, β-is no
Saturated carboxylic acid is preferably selected from cinnamic acid, crotonic acid, fumaric acid, itaconic acid, maleic acid, acrylic acid and/or methacrylic acid, especially
It is preferred that acrylic acid and/or methacrylic acid, especially acrylic acid.
It in the method according to the invention, can be mixed as the copolymer or copolymer being used in the water-based composition of sealing
Other comonomers for closing the other components of object can be selected from α, the ester of beta-unsaturated carboxylic acid, have not in preferred aliphat functional group
More than the acrylic acid of 12 carbon atoms and/or the linear or branched alkyl group ester of methacrylic acid.It is movable due to polymer backbone
Property (mobility) increase, this comonomer improves solidification on the metal base with oxide protective layer and/or dry
The adhesiveness of the dry composition for sealing, this promotes orientation of the affine acidic group in surface to oxide and metal surface again.
Especially low acid value copolymer of the acid value less than 100mg KOH/g has this effect.Usually, it has been shown that the copolymer
Or the low acid value of copolymer mixture can improve solidification and/or the dry composition for sealing when being exposed to water-bearing media
Barrier properties.Therefore it is preferred according to the present invention that additionally comprising above-mentioned comonomer and acid value is less than 100mg KOH/g, it is special
It is not less than the copolymer or copolymer mixture of 60mg KOH/g.
In order to obtain good film forming during the solidification composition for being used for sealing, dissolves and/or be dispersed in
Copolymer in water, or dissolving and/or the copolymer mixture that is dispersed in water need to be changed into after water phase volatilization it is molten
Melt state.In order to meet this requirement, the glass transition temperature of preferred copolymer or copolymer mixture is no more than 80 DEG C, special
It You Xuanbuchaoguo not be 60 DEG C.Be made of alkene and alpha, beta-unsaturated carboxylic acid, weight average molecular weight MwCopolymerization no more than 20,000u
Object or copolymer mixture usually have this property, therefore, according to the method for the present invention in the combination for sealing
Object preferable weight-average molecular weight is no more than 20,000u, especially no more than the copolymer or copolymer mixture of 15,000u.
In a preferred method, the copolymer for dissolving and/or being dispersed in water or dissolving and/or what is be dispersed in water be total to
The acidic group of copolymer mixture exists in the composition for sealing in the form of being at least partially neutralized.This measure carries
The high ability of copolymer self-emulsifying in water phase, this often leads to the relatively small particle of film forming organic component, and then causes more
Effectively seal against the hole of protective layer.Therefore, neutralization reagent is preferably additionally present in described for the composition of sealing.
Preferably, preferably with powdered ammonia, amine, metallic aluminium and/or zinc and element Li, Na, K, Mg, Ca, Fe (II) and
The water-soluble oxide and hydroxide of Sn (II) is applicable neutralization reagent, and in a preferred method, they are extraly present in
In the composition for sealing.Those skilled in the art are in this regard, it is realized that the neutralization reagent is used for described
The component of the composition of sealing carries out neutralization reaction to keep the function of neutralization reagent, therefore only can be in the form of reaction product
Indirect detection they.For example, metallic aluminium or zinc powder react in water phase generates corresponding hydroxide, hydrogen is generated, it is described
Hydroxide leads to the neutralization of the acidic group of copolymer or copolymer mixture again so that finally there was only the sun of the element aluminum or zinc
Ion is detectable.Therefore, the neutralization reagent only is understood as in the corresponding composition for sealing being used as matching
Auxiliary agent processed.
Ammonia and amine is particularly preferred neutralization reagent because they application for sealing composition because heat supply and
Cured period can be transformed into gas phase, therefore would not remain in cured sealing.It can be used as the water-based composition for sealing
In neutralization reagent amine be preferably morpholine, hydrazine, azanol, monoethanolamine, diethanol amine, triethanolamine, dimethylethanolamine and/
Or diethyl ethylene diamine.
The degree of neutralization of the acidic group of copolymer or copolymer mixture is preferably at least 20%, particularly preferably at least 30%
Acidic group exists in the form of being neutralized.In the preferred embodiment of this method, copolymer or copolymer mixture should be avoided
Height of the acidic group higher than 50% neutralizes, because this can cause significant percentage of copolymer or copolymer mixture molten in water
Solution, and very high viscosity is generated, this is unfavorable for applying the composition for sealing.
In general, in order to keep the best rheological property of the composition for sealing, 1g copolymers or copolymer are based on
The amount of mixture, the neutralization reagent being added preferably in the formulation makes the existing amount of neutralization reagent be at least 4/z μm of ol,
Preferably at least 6/z μm of ol is respectively multiplied by the acid value of copolymer or copolymer mixture, but preferably more than 10/z μm of ol, especially
Preferably more than 8/z μm of ol is multiplied by the acid value of copolymer or copolymer mixture.Divisor z is natural number, corresponds to neutralization reaction
Equivalent value.Acidic group rubs in copolymer or copolymer mixture that 1 mole of neutralization reagent of the equivalent value expression can neutralize
That number.
Water-based composition for sealing needs to include crosslinking agent, and according to the present invention, which must be adapted for being crosslinked
The copolymer or copolymer mixture are formed compared with the copolymer or copolymer mixture with higher molecular weight
Network.Described crosslinking agent itself can by in the copolymer or copolymer mixture and/or free acid base is formed covalently
Or coordinate bond and form crosslink sites, can be connected by the different copolymer object of the copolymer or the copolymer mixture
It connects or it may be crosslinked in catalytic molecular, such as acid anhydrides is formed in the molecule by cracking hydrone.
It has discovered that by crosslinking agent and forms the network with higher molecular weight, the crosslinking agent is with covalent or coordination side
Formula is attached in polymer backbone, is conducive to effectively seal against the oxide protective layer to resist Korrosionsmedium.Therefore, according to
Water-soluble inorganic compound and/or water solubility and/or water dispersible of the currently preferred crosslinking agent selected from element Zr and/or Ti
Aminoplast and/or carbimide.If in 20 DEG C of deionized water (κ<1μScm-1) in apply 1 minute energy input be per second
Every liter 103Joule shearing force after, average grain diameter is less than 1 μm, then the crosslinking agent based on organic compound be it is water-soluble and/
Or water dispersible.Average grain diameter can be according to ISO 13320:2009 by laser diffraction by cumulative particle size distribution with so-called
D50 values determine.
The applicable crosslinking agent of water-soluble inorganic compound based on element Zr and/or Ti is selected from alkoxide and/or carbonate, special
Not preferred tetrabutyl zirconate hydrochlorate, zirconium-n-propylate hydrochlorate, four titanium butoxide hydrochlorates, four titanium propanolate hydrochlorates, zirconium carbonate ammonium salt
And/or titanium carbonate ammonium salt, particularly preferred zirconium carbonate ammonium salt.If be based on respective element Zr and/or Ti, compound at 20 DEG C
Deionized water (κ<1μScm-1) in solubility be at least 1g/L, then it is assumed that these compounds are water-soluble.
In order in the method and step ii of the water soluble compound based on element Zr and/or Ti) in realize the copolymer or
Full cross-linked, the weight ratio for being determined as element Zr and/or Ti of the weight ratio of preferably this crosslinking agent of copolymer mixture
Example, the dimensionless acid of solid content divided by copolymer or copolymer mixture based on the copolymer or copolymer mixture
Value (in terms of gram KOH/g) is more than 0.04XZr+0.02·XTi.Conversely, the preferably weight ratio divided by copolymer or nothing
The dimensionless acid value (in terms of gram KOH/g) for advising copolymer mixture is less than 0.12XZr+0.06·XTi, to obtain stable use
In the composition of sealing.XZrAnd XTiIt is the corrresponding quality score of element Zr or Ti, element Zr's and Ti based on the crosslinking agent
Toatl proportion.
In the preferred embodiment of this method, the crosslinking agent is based in method and step ii) in cause copolymer or
The organic compound of copolymer mixture covalent cross-linking, therefore it is in particular selected from water dissolvable and/or water dispersible aminoplast
And/or carbimide.
Particularly suitable aminoplast crosslinking agent is to be based on melamine, urea, dicyandiamide, guanamines and/or guanidine.Especially
Ground, melamine resin are preferred aminoplast crosslinking agent, formaldehyde：The molar ratio of melamine is preferably greater than 1.5.
Alternatively or additionally existing, the crosslinking agent in the composition for sealing is carbon imidodicarbonic diamide.Carbon two
Acid imide includes the imidodicarbonic diamide structural unit of at least one-C=N=C- types.It is preferable, however, that they are polyfunctional, every point
The imidodicarbonic diamide equivalent weight of sub- diimide group is the 300-500 grams of polyfunctional compound.In particular it is preferred to carbon two
Acid imide is the especially logical formula (I) by decarboxylic reaction derived from the isocyanates comprising at least two isocyanate groups
Those of：
Wherein n：The natural integer of 1-20；
R1：Including no more than the aromatics of 16 carbon atoms, aliphatic or acyclic functional group.
Preferably, the isocyanate groups are closed by hydrophilic blocking group, and hydrophilic protecting group itself imparts two acyl of carbon
The better water dispersible of imines or water solubility.Applicable hydrophily blocking group is, for example, hydroxyalkylated sulfonic acid, hydroxyalkylphosphonic acids,
Hydroxyalkyl phosphoric acid, polyethylene glycol and tertiary or quaternary ammonium alkylol or aminoalkyl amine.
In particularly preferred embodiments, the crosslinking agent of the composition for sealing is therefore selected from different comprising closing
The carbon imidodicarbonic diamide of cyanic acid ester terminal, chemical general formula are formula (II)：
Wherein, n：The natural integer of 1-20；
R1：Including no more than the aromatics of 16 carbon atoms, aliphatic or acyclic functional group.
X:-NH-R1-N(R1)2、-O-R1-N(R1)2、-NH-R1-N(R1)3Y、-O-R1-N(R1)3Y、-O-R1-SO3Z、-O-
R1-O-PO3Z、-O-R1-PO3Z、-O-(C2H4)p-OH、-O-(C3H6)p-OH。
Wherein, Y：Hydroxide, chloride, nitrate, sulfate；
Wherein, Z：Hydrogen, ammonium, alkali or alkaline earth metal；
Wherein, p：The natural integer of 1-6.
The preferred diisocyanate of the corresponding carbon imidodicarbonic diamide generated by decarboxylation is, for example, two isocyanide of hexa-methylene
Acid esters, hexamethylene -1,4- diisocyanate, eylylene diisocyanate, isophorone diisocyanate, dicyclohexyl first
Alkane -4,4- diisocyanate, methylcyclohexane diisocyanate and tetramethyl xylylen diisocyanate, 1,5- naphthylenes
Diisocyanate, 4,4- methyl diphenylene diisocyanates, 4,4- diphenyldimethyhnethanes diisocyanate, 1,3- phenylenes
Diisocyanate, 1,4- phenylene vulcabonds, 2,4- inferior cresyl vulcabonds, 2,6- xylene diisocyanates
Ester.
In principle, preferably organic crosslinking agent, especially aminoplast and/or carbimide, weight average molecular weight MwDo not surpass
2,500u are crossed, is particularly preferably no more than 1,500u, it is full cross-linked with the copolymer or copolymer mixture to ensure.
It is aqueous in step (i) in a particularly preferred embodiment of the method according to the present invention for sealing
Composition includes：
A) 0.5-15 weight %, the preferably above-mentioned copolymer of 2-10 weight % or copolymer mixture；
B) 0.5-10% weight, preferably 1-6 weight % based on water-soluble and/or water dispersible aminoplast and/or carbon
Imido crosslinking agent；
C) it is no more than the neutralization reagent of 6 weight %, is selected from ammonia and/or amine, preferably alkanolamine；
D) it is no more than 6 weight %, but the thickener of more preferably at least 0.1 weight %, selected from the poly- of not representation compound a)
Object organic compound is closed, polyacrylate is preferably selected from, the acid value of free acid is more than 200mg/g KOH；
E) it is no more than other auxiliary agents of 5 weight %, is preferably selected from corrosion inhibitor, levelling agent, stabilizer, surface-active
Agent and pigment are the generally known to those skilled in the art of coating formulation field；With
F) it is less than the organic solvent of 5 weight %.
In a preferred method according to the invention, the contact in step (i) is applied by using spraying or dip-coating method
Add the wet film for the water-based composition of sealing and carry out, preferably by dipping method, wherein after termination, preferably directly
Excessive wet film is directly removed before connecing before step (ii), to form the wet film of uniform film thickness adherency.
The termination contacted by dip-coating is carried out for example, by removing metal base or reducing liquid level.It can be by making
It is dripped, or is blown off, or it is squeezed out from metal base and removes excessive wet film.The combination for sealing
The preparation of object makes oxide protective layer be subjected to most preferably soaking, therefore above-mentioned conventional coating techniques can carry out without difficulty, and
And special technical measures are not needed.Although for example, it is possible to carry out contact by vacuum impregnation, this not necessarily can be real
Now satisfactory sealing.
During method and step i), the composition for sealing and the metal base with the oxide protective layer
Time of contact is at least 1 second, preferably at least 10 seconds.However, the reason of for step economy, the time of contact does not preferably surpass
120 seconds are spent, is particularly preferably no more than 60 seconds.
According to the present invention in the method for sealing, it is described load have the metal base of oxide protective layer with comprising at
It is to be used for cured method and step after the contact of the water-based composition of membrane polymer.In a preferred method, provide thermal energy with
So that the peak temperature of the base material is measured as at least 120 DEG C, particularly preferably at least 160 DEG C, but preferably smaller than 200 DEG C of base material
Peak temperature (so-called peak metal temperatures).
Furthermore it is preferred that in step ii) after, the organic component of the water-based composition for sealing is retained in oxide protective layer
On amount make in complete thermal decomposition, every square metre of release at least 1g CO2, preferably at least 4g CO2, but it is no more than 20g
CO2.When pyrolysis temperature is kept for the sufficiently long time, pyrolysis can be completed at 500 DEG C, air (so-called " gas is provided
Change ").
In a preferred method, with the oxide protective layer metal base be selected from aluminium, magnesium and/or titanium, preferably aluminium and/
Or magnesium, particularly preferably aluminium and its alloy, wherein the element of the specific base material account for the alloy of these base materials it is at least 50 former
Sub- %.It is preferred that the reason of these base materials, is these base materials to the film-forming organic polymer that is present in the composition for sealing
Special compatibility and its for anticorrosion initial treatment to form the conventional skill of the oxide protective layer with high porosity
Property in art method so that these base materials are sealed immediately after this anticorrosion initial treatment especially important.
In advantageous variant according to the method for the present invention, wherein the metal base is selected from aluminium and/or magnesium, the oxidation
Protective layer is substantially made of the oxide and/or hydroxide of elements Si, Ti and/or Zr.Under any circumstance, as the guarantor
When nonmetallic ratio in sheath is less than 10 atom %, and the ratio of elements Si, Ti and Zr is based on all metals in protective layer
Toatl proportion be at least 30 atom %, when preferably at least 50 atom %, the protective layer is substantially by the oxide of these elements
And/or hydroxide composition.
This oxide protective layer on base material aluminium and magnesium can be obtained by electrolytic method.Particularly, wherein base material at least portion
Divide the electrolytic method connected as anode, water soluble compound of the electrolyte comprising elements Si, Ti and/or Zr, and fits
For providing the substantially oxide protective layer made of the oxide and/or hydroxide of elements Si, Ti and/or Zr.If its
In deionized water (κ at 20 DEG C<1 μ Scm-1) in solubility be at least 1g/L, be based on corresponding elements Si, Ti and/or Zr,
The component composition being then used in the electrolyte of deposited oxide protective layer is regarded as water-soluble.
Particularly, the electrolytic method being wherein at least partly applied on the base material for depositing the voltage of protective layer
It is applicable, the voltage is higher than the decomposition voltage of the aqueous electrolyte, wherein the base material is connected as anode, and preferably
Ground, when applying voltage to deposit protective layer, the average voltage of application is at least 50V, especially preferably at least 200V.It is such
Method is known to the skilled in the art plasma electrolysis method (WO2003/029529A1, WO2006/ in the prior art
047501)。
On the other hand, therefore the present invention includes the anti-corrosive treatment method for the metal base for being selected from aluminium and/or magnesium, wherein：
(1) metal base and the aqueous electrolyte of the water soluble compound comprising elements Si, Ti and/or Zr is made to contact, and
During the contact, apply the voltage for depositing protective layer at least partly on the substrate, is higher than aqueous electrolysis
The decomposition voltage of matter, wherein the base material is connected as anode, and preferably when applying voltage to deposit protective layer, application is put down
Equal voltage is more preferably at least 50V, especially preferably at least 200V；
(2) in the case of the flushing and drying steps being inserted into or without centre, make that there is the protective layer
Metal base is contacted with the water-based composition for sealing, is measured by 4mm DIN flow cups, the water-based composition for sealing
Flowing time is no more than 50 seconds, and the water-based composition for sealing includes：
A) water-dispersed and/or water dissolution form at least one aliphatic and acyclic olefin and at least one α, β-unsaturation
The copolymer or copolymer mixture of carboxylic acid, wherein the acid value of the copolymer or copolymer mixture is at least 20mg KOH/
G, but it is no more than 200mg KOH/g；With
B) crosslinking agent；
And then
(3) wet film that is dry in the case where providing thermal energy and/or being crosslinked applied in step (2).
The above-mentioned preferred embodiment of method according to the present invention for sealing is also similarly anti-for metal base
The preferred embodiment of method and step (2) and (3) of the method for the present invention of corrosion treatment.
The invention also includes use comprising at least one aliphatic water-dispersed and/or water dissolution form and acyclic olefin with
On the water-based composition of the copolymer of at least one alpha, beta-unsaturated carboxylic acid or copolymer mixture sealing aluminium base based on member
The oxide of plain Si, Ti and/or Zr and/or the protective layer of hydroxide, wherein the acid value of the copolymer or copolymer mixture
At least 20mg KOH/g, but it is no more than 200mg KOH/g, and in the copolymer or copolymer mixture of the water-dispersible form
Acidic group at least 20%, but exist with the state that is neutralized no more than 60%, wherein the thickness of the protective layer is at least 2 μ
m.The protective layer is preferably based on the oxide and/or hydroxide of element ti, and density is less than 3.5g/cm3。
Under any circumstance, when the nonmetallic ratio in the protective layer is less than 10 atom %, and element in protective layer
The ratio of Ti, based on the toatl proportion of all metals, at least 30 atom %, and when more preferably at least 50 atom %, the protection
Oxide and/or hydroxide of the layer based on element ti.
The density of protective layer is defined as with g/cm2Layer structure for unit divided by the layer thickness as unit of cm, wherein institute
It states layer structure and determines poor (the unit g/ of weight per unit area of aluminium sheet before and after applying the protective layer by testing
cm2), the ratio of weight per unit area difference caused by due to the dissolving of aluminium base is subtracted, again by before applying the protective layer
The proportional difference of the aluminium dissolved in the liquid medium of the wet chemical method later determines.This special protection layer is applied
Most common wet chemical method on to aluminium is electrolysis, preferably plasma electrolysis method.
Exemplary implementation scheme：
Aluminium sheet (the AA6014 coated by plasma electrolysis is sealed using the formulation in table 1；It is obtained by Chemetall
The test board arrived).
For this purpose, the aluminium sheet of initial cleanness and degreasing is being included 4.5g/L phosphoric acid and 12g/L hexafluoro titaniums under 435V voltages
Constant potential coats 3 minutes in the electrolyte (pH value 2.5) of acid.The layer of the obtained protective layer based on titanium oxide and titanium hydroxide
Thickness is 10-12 μm, (has by eddy current probe according to DIN-ISO 2360 and measures probe ED10's
MP40E-S；Fischer it) measures.
Then the plank so coated is immersed in formulation A to C 30,60 or 120 seconds, then suspension 1 minute so as to
Liquid drips.Retain wet film on a metal plate after drip in stove to cure 2 minutes at 230 DEG C.According to above-mentioned eddy-current method
After measurement, the thickness of cured sealant is about 8 μm.
Table 1 includes the aqueous formulations A to C for sealing of ethylene-acrylic acid copolymer
1Alkaline carbonic acid zirconium ammonium salt solution (20 weight %Zr)
2Melmac (20 minutes dry at 230 DEG C)
3Thickener, pH value 2.5；According to ISO 2555,30-70mPas；
According to DIN EN ISO 9227, CASS tests are carried out to the aluminium sheet of the plasma electrolysis coating of the sealing
(240 hours).After load time, all sealing metal plates are all 0 according to the blistering degree of DIN EN ISO 4628-1
(S0) (0 (S0) to 5 (S5)) is up to 1 (0 to 5) according to the degree of rusting of DIN EN ISO 4628-3.Unencapsulated plasma
The degree of rusting for being electrolysed the aluminium sheet of coating is 5.
Claims (13)
1. the method for the oxide protective layer on sealing metal base material, it is characterised in that make to have the metal base of protective layer with it is following
Substance contacts：
(i) it is used for the water-based composition of sealing, it includes
A) be based on the water-based composition, at least one aliphatic water-dispersed and/or water dissolution form of at least 1 weight % and
Acyclic olefin and at least one α, the copolymer or copolymer mixture of beta-unsaturated carboxylic acid, wherein the copolymer or copolymer
The acid value of mixture is at least 20mg KOH/g, but is no more than 200mg KOH/g；With
B) crosslinking agent,
And then
(ii) it is dried and/or cures in the case where providing thermal energy,
Wherein, it is measured using 4mm DIN flow cups, described in step (i) not for the flowing time of the water-based composition of sealing
More than 50 seconds.
2. according to the method described in claim 1, it is characterized in that being based on the water-based composition, the copolymer or copolymer
The ratio of mixture is at least 5 weight %, but preferably more than 30 weight %, is particularly preferably no more than 20 weight %.
3. according to the one or more methods of preceding claims, it is characterised in that be selected from member according to the crosslinking agent of component b)
The water-soluble inorganic compound of plain Zr and/or Ti, water-soluble and/or water dispersible aminoplast and/or carbimide.
4. according to the one or more methods of preceding claims, it is characterised in that for sealing described in step (i)
The copolymer of water-based composition or the aliphatic of copolymer mixture and acyclic olefin are selected from ethylene, propylene, 1- butylene, 2- fourths
Alkene, isobutene, 1,3-butadiene and/or 2- methyl-1s, 3- butadiene, particularly preferred ethylene and/or propylene.
5. according to the one or more methods of preceding claims, it is characterised in that for sealing described in step (i)
The copolymer of water-based composition or the alpha, beta-unsaturated carboxylic acid of copolymer mixture are selected from cinnamic acid, crotonic acid, fumaric acid, clothing health
Acid, maleic acid, acrylic acid and/or methacrylic acid, preferably acrylic acid and/or methacrylic acid, particularly preferred acrylic acid.
6. according to the one or more methods of preceding claims, it is characterised in that the water-based composition for sealing
In copolymer or copolymer mixture acidic group at least 20%, preferably at least 30%, but be no more than 60%, and preferably do not surpass
50% is crossed in the form of being neutralized to exist.
7. according to the one or more methods of preceding claims, it is characterised in that the contact in the step (i) is logical
It crosses spraying or dip-coating method applies the wet film of the water-based composition for sealing and carries out, preferably by dip-coating method,
Wherein, after, preferably excessive wet film is removed before the step (ii) immediately after which, to be formed with uniform films
The wet film of thickness adherency.
8. according to the one or more methods of preceding claims, it is characterised in that the metal base be selected from aluminium, magnesium and/
Or titanium, preferably aluminium and/or magnesium, particularly preferred aluminium.
9. according to the one or more methods of preceding claims, it is characterised in that the oxide protective layer is substantially by member
The oxide and/or hydroxide of plain Si, Ti, Zr, Nb, Ta and/or Sn are made, as long as and the metal base be selected from aluminium and/
Or magnesium, then its be preferably made of the oxide and/or hydroxide of elements Si, Ti and/or Zr.
10. according to the one or more methods of preceding claims, it is characterised in that the offer heat in step (ii)
The peak temperature of the base material can be caused to be at least 120 DEG C, especially preferably at least 160 DEG C, but preferably shorter than 200 DEG C (PMT,
So-called peak metal temperatures).
11. according to the one or more methods of preceding claims, it is characterised in that in step ii) after, it stays in described
The amount of the organic solid component of the water-based composition for sealing on oxide protective layer made in complete the case where being pyrolyzed
Lower releasable at least 1g CO2, preferably at least 4g CO2, but it is no more than 20g CO2。
12. water-based composition is used to seal the oxide and/or hydroxide based on elements Si, Ti and/or Zr on aluminium base
Protective layer purposes, the water-based composition includes at least one aliphatic water-dispersed and/or water dissolution form and acyclic
Alkene and at least one α, the copolymer or copolymer mixture of beta-unsaturated carboxylic acid, wherein the copolymer or copolymer mixing
The acid value of object is at least 20mg KOH/g, but is no more than 200mg KOH/g, and the copolymer or copolymer of the water-dispersible form
At least 20% of acidic group in mixture, but exist with the state being neutralized no more than 60%, wherein the thickness of the protective layer
It is at least 2 μm.
13. purposes according to claim 12, it is characterised in that oxide and/or hydrogen of the protective layer based on element ti
Oxide, and density is less than 3.5g/cm3。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102015208076.5 | 2015-04-30 | ||
| DE102015208076.5A DE102015208076A1 (en) | 2015-04-30 | 2015-04-30 | Method for sealing oxidic protective layers on metal substrates |
| PCT/EP2016/059465 WO2016174122A1 (en) | 2015-04-30 | 2016-04-28 | Method for sealing oxide protective layers on metal substrates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108541265A true CN108541265A (en) | 2018-09-14 |
Family
ID=56014959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680024282.6A Pending CN108541265A (en) | 2015-04-30 | 2016-04-28 | The method of oxide protective layer on sealing metal base material |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20180037748A1 (en) |
| EP (1) | EP3289010B1 (en) |
| CN (1) | CN108541265A (en) |
| DE (1) | DE102015208076A1 (en) |
| ES (1) | ES2748355T3 (en) |
| WO (1) | WO2016174122A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101048277A (en) * | 2004-10-25 | 2007-10-03 | 亨克尔两合股份公司 | Article of manufacture and process for anodically coating an aluminum substrate with ceramic oxides prior to organic or inorganic coating |
| CN103619974A (en) * | 2011-03-31 | 2014-03-05 | 汉高股份有限及两合公司 | Coating formulation for the interior surfaces of cans |
| DE102012223356A1 (en) * | 2012-12-17 | 2014-06-18 | Henkel Ag & Co. Kgaa | Process for producing coated can ends |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE507657A (en) | 1950-12-06 | |||
| US3181461A (en) | 1963-05-23 | 1965-05-04 | Howard A Fromson | Photographic plate |
| GB1126855A (en) * | 1966-03-01 | 1968-09-11 | Honny Kasei Kabushiki Kaisha H | Improvements in or relating to aluminium articles having an electro-deposited resin surface coating of high durability |
| DE3316348C2 (en) * | 1983-05-05 | 1985-03-07 | PTG Plasma-Oberflächentechnik GmbH, 7240 Horb | Process for coating a workpiece |
| DE3434668A1 (en) * | 1984-09-21 | 1986-04-03 | Henkel KGaA, 4000 Düsseldorf | PRESERVATIVES FOR ALUMINUM SURFACES |
| DE19621819A1 (en) * | 1996-05-31 | 1997-12-04 | Henkel Kgaa | Short-duration hot seal process for anodised metal surfaces |
| DE19858034A1 (en) * | 1998-12-16 | 2000-06-21 | Henkel Kgaa | Improved compaction process for anodized metal surfaces |
| JP2003034894A (en) | 2001-07-25 | 2003-02-07 | Kobe Steel Ltd | Al ALLOY MEMBER SUPERIOR IN CORROSION RESISTANCE |
| US7452454B2 (en) | 2001-10-02 | 2008-11-18 | Henkel Kgaa | Anodized coating over aluminum and aluminum alloy coated substrates |
| US6916414B2 (en) * | 2001-10-02 | 2005-07-12 | Henkel Kommanditgesellschaft Auf Aktien | Light metal anodization |
| JP4389066B2 (en) * | 2003-08-29 | 2009-12-24 | 三井化学株式会社 | Water-dispersed rust-proof coating composition |
| US20050252165A1 (en) * | 2004-02-02 | 2005-11-17 | Hubbell David A | Fiber reinforced metal construct for reduced fatigue and metal embrittlement in susceptible structural applications |
| EP1873278A1 (en) | 2006-06-30 | 2008-01-02 | Henkel Kommanditgesellschaft Auf Aktien | Silicate treatment of sealed anodised aluminum |
| US8039116B2 (en) * | 2007-08-08 | 2011-10-18 | General Electric Company | Nb-Si based alloys having an Al-containing coating, articles, and processes |
| KR20140035935A (en) | 2011-06-15 | 2014-03-24 | 헨켈 아게 운트 코. 카게아아 | Method and apparatus for reducing emissions and/or reducing friction in an internal combustion engine |
-
2015
- 2015-04-30 DE DE102015208076.5A patent/DE102015208076A1/en not_active Withdrawn
-
2016
- 2016-04-28 EP EP16723271.9A patent/EP3289010B1/en active Active
- 2016-04-28 WO PCT/EP2016/059465 patent/WO2016174122A1/en active Application Filing
- 2016-04-28 CN CN201680024282.6A patent/CN108541265A/en active Pending
- 2016-04-28 ES ES16723271T patent/ES2748355T3/en active Active
-
2017
- 2017-10-20 US US15/789,186 patent/US20180037748A1/en not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101048277A (en) * | 2004-10-25 | 2007-10-03 | 亨克尔两合股份公司 | Article of manufacture and process for anodically coating an aluminum substrate with ceramic oxides prior to organic or inorganic coating |
| CN103619974A (en) * | 2011-03-31 | 2014-03-05 | 汉高股份有限及两合公司 | Coating formulation for the interior surfaces of cans |
| DE102012223356A1 (en) * | 2012-12-17 | 2014-06-18 | Henkel Ag & Co. Kgaa | Process for producing coated can ends |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2748355T3 (en) | 2020-03-16 |
| US20180037748A1 (en) | 2018-02-08 |
| EP3289010B1 (en) | 2019-07-24 |
| WO2016174122A1 (en) | 2016-11-03 |
| EP3289010A1 (en) | 2018-03-07 |
| DE102015208076A1 (en) | 2016-11-03 |
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